CN109187457A - A kind of preparation method of the fluorescent test paper for TNT detection - Google Patents
A kind of preparation method of the fluorescent test paper for TNT detection Download PDFInfo
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- CN109187457A CN109187457A CN201810942887.4A CN201810942887A CN109187457A CN 109187457 A CN109187457 A CN 109187457A CN 201810942887 A CN201810942887 A CN 201810942887A CN 109187457 A CN109187457 A CN 109187457A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
A kind of preparation method of the fluorescent test paper for TNT detection, the preparation process of the fluorescent test paper includes following three step: first, in a nitrogen atmosphere, sodium hydrogen telluride precursor solution is prepared for tellurium powder, deionized water and sodium borohydride respectively using sulfydryl Aqueous phase, it is reacted again with cadmium sulfide and sodium hydroxide with above-mentioned precursor solution, obtains CdTe@CdS quantum dot；Then, make CdTe@CdS quantum dot coated with zinc oxide shell by the method for hydrolyzing zinc acetate and modifies mercaptoethylmaine, surface is obtained with amino CdTe@CdS@ZnO quantum dot fluorescence probe, finally, CdTe@CdS@ZnO quantum dot fluorescence probe is immersed in chemical test paper, after natural drying, it is cut into different shape and size paper tape, be saturated in test paper with large specific surface area, recognition site is more, selectivity is good and the quantum dot fluorescence probe of high sensitivity, obtained to TNT molecule have identification and detection fluorescent test paper.
Description
Technical field
The present invention relates to materials science fields, in particular to have the preparation method to the trace TNT fluorescent test paper detected.
Background technique
Fluorescence sense technology belongs to chemical sensitisation scope, and with highly sensitive, highly selective, high reliability and easily portable
The characteristics such as property, show one's talent in numerous explosives detection techniques.1970s, i.e., when just having found quantum dot, about it
Application be limited only to photoelectric material and microelectronic field in terms of.In recent years, due to the unique characteristics of luminescence of quantum dot, make it
It is more and more widely used detection in trace explosive, and rapidly becomes the hot spot studied both at home and abroad.With the day of science and technology
Crescent is different, emerges one after another about the method for nitryl aromatic race explosive detection, as Li Jing rainbow research group of Tsinghua University invents
A kind of sensor that electrochemistry-colorimetric is compound out, by the way that ionic liquid is covered on the surface ITO, to the explosion containing different nitros
Object carries out selective enrichment and is then restored by explosive of the electrochemical method to enrichment, then pass through optical imaging device
By the color decomposition of reduzate be three color of red, green, blue (Red, Green, Blue, RGB), formed rgb light spectrum (JACS, 2009,131(4): 1390-1391).Since the reduzate of different explosives shows feature rgb light spectrum, this method is to nitro
Explosive TNT sensitivity with higher and selectivity.But the explosive being detected in this method cannot be enriched with completely, be processed
Journey is cumbersome, and Optical devices used in detection process must be very sensitive, and operator needs to have the special of optics aspect
Industry knowledge, accordingly, it is difficult to promote the use of on a large scale.
Since the short of electricity sub-feature of nitro explosive easily causes electronics transfer and generates Resonance energy transfer, so as to cause
Therefore the variation of fluorescence intensity causes the very big interest of people with fluorescence chemical sensor detection nitro compound in recent years,
And there is faster development.Most typical is exactly that biological antibody and enzyme are connected on semiconductor-quantum-point by Ellen et al., with exploitation
Solution phase nanometer based on fluorescence resonance energy transfer (Fluorescence Resonance Energy Transfer, FRET)
Grade sensing component, in aqueous environments specific detection explosivity 2,4,6-trinitrotoluene (TNT) (JACS, 2005,127(18): 6744-6751).Hybrid sensor is made of anti-TNT specific Ab fragments, is connected to by the affine coordination of metal
On hydrophily quantum dot.The TNT analog of dye marker in antibody combining site combines in advance, and quantum dot is quenched by FRET
Luminescence generated by light.Although such method can use biological antibody and enzyme with specific detection TNT, to detection environmental requirement
It is higher, under the conditions of high temperature and pressure strong acid and strong base, antibody and enzyme easy in inactivation.
In the fluorescence analysis method of the trace explosive detection developed in recent years, with semiconductor-quantum-point and possess very high
Fluorescence quantum yield fluorescence doped nano particle shows that huge development is latent as the chemical/biological sensors of optical unit
Power.Most of work at present mainly by fluorescent molecule with it is glimmering caused by the intermolecular generation electronics transfer of explosive or energy transfer
Optical quenching and realize.The analysis method has extensive work report for the detection of trace explosive.Working principle is that do not having
In the case where having explosive molecule, after fluorescent molecule absorption photon (hv) transition generation exciton, exciton return ground state generation fluorescence
(hv).In the presence of explosive molecule, fluorescent molecule is excited the exciton generated and passes through electronics transfer transition or energy transfer transition
The excitation state of explosive molecule is passed to, fluorescent molecule ground state is then back to by it again.The process companion of electronics or energy transfer
With fluorescent quenching, achieve the purpose that trace explosive Molecular Detection.Institute of Chemistry, Academia Sinica researcher report
A kind of simple but sensitive method (Angew. Chem. Int. Ed, 2008,47(45): 8601-8604), by using gold
Nano particle judge that the colorimetric of the TNT of pM level can with the naked eye, by using gold nanoparticle (AuNPs), and utilize Jenner
Donor-acceptor interaction on rice corpuscles/solution interface between TNT and cysteamine successfully develops a kind of novel simple
The measurement of direct color comparison imaging TNT.Although this method high sensitivity is limited due to gold nano nature
Its application in complex matrices actual sample.Nie Dongxia et al. passes through the combination of molecular imprinting technology and sensing technology,
Using gold nano grain as carrier, a kind of New Two Dimensional molecular imprinting electrochemical sensor is studied and is prepared for and applied to TNT's
Specificity and sensibility detection (Chinese outstanding doctoral dissertations full-text database, 2011).Although this method can be to TNT
Specificity detection, but the gold nanoparticle as carrier is difficult the purpose for being implemented in combination with its self assembly for controlling it with template,
It cannot efficiently apply.Far away from quantum dot fluorescence probe, under similar reaction condition, functionalized semiconductor quantum
The preparation time of point fluorescence probe is shorter.Quantum dot fluorescence probe has the fluorescence property of high quality, splendid water solubility, well
Stability, be easy to functional modification, high selection and highly sensitive detection feature, be the detection hand rare to explosive detection
Section.
With the continuous development to semiconductor-quantum-point fluorescent probe technique, people deepen continuously to quantum dot research, have
There is the semiconductor-quantum-point of unique characteristics of luminescence to rapidly become the focus studied both at home and abroad for detecting trace explosive.Chinese section
Hefei intelligent machine research institute of institute Zhang Zhongping project has been combined into ZnS doping Mn2+The mercaptoethylmaine of quantum dot, surface modification can
Specificity, which identifies, and binding molecule is eventually by the electronics transfer between quantum dot and target analytes TNT makes the orange of quantum dot
Color fluorescent quenching, thus achieve the purpose that detect TNT (Anal. Chem, 2008,80(9): 3458-3465).California, USA is big
The researchs such as Chen Wei are combined with pyrene functionalized ruthenium nano particle (RuNPs), for detecting nitryl aromatic explosive.Pyrene
The modification of group expands the conjugated system inside ruthenium nano particle, thus keep the energy electron transfer efficiency of sensor higher,
Increase to TNT detection limit (Anal. Chem, 2010,82(2): 461-465).Tight show equality has studied a kind of have and divides
The advantages of room temperature phosphorimetry sensor of sub- trace, the room temperature phosphorimetry performance and molecular engram of Mn doping ZnS quantum point, combines,
So that the performance of sensor it is more excellent (Anal. Chem, 2009,81(4): 1615-1621).Feng Lijuan et al. is by matching
There is the preparation of body exchange process 8-hydroxyquinoline (HQ) amine to block layer (ZnS-NH2- QNPs) functionalization ZnS nanoparticle, with
TNT effect, ZnS-NH2Amino on the surface-QNPs can be by forming Meisenheimer (Meisenheimer) compound in conjunction with molten
TNT molecule in liquid, reach to the quantitative detection of target analytes TNT molecule (Dyes and Pigments, 2013,97(1):
84-91).Kui etc. is respectively using transmitting is red and two kinds of various sizes of CdTe quantums of green fluorescence, by by dioxy
SiClx nano particle is embedded in the quantum dot of red emission, and by the quantum dot of green emitted by being covalently bonded to titanium dioxide
Silicon face hybridization is to form double transmitting fluorescent hybridization nano particles.The fluorescence of red quantum dot is kept in nano SiO 2 particle
It is constant, and can be by forming Meisenheimer (Meisenheimer) compound selectivity with the green quantum dot of polyamine functional
Ground combination TNT, causes green fluorescence to quench by Resonance energy transfer, realize to the detection of TNT (JACS, 2011,133(22):
8424-8427).Formation of the Cai Qingyun based on the Meisenheimer compound between TNT and cysteine, by using L-
The CdTe quantum (QDs) of cysteine sealing end measures TNT, and the electronics of CdTe QDs passes through Meisenheimer (Meisenheimer)
The formation of compound is transferred to TNT molecule, is quenched the fluorescence of quantum dot, achievees the purpose that detect TNT
(Nanotechnology, 2010,21(12): 125502).
Above-mentioned detection method advantage is a lot of, but complex steps, and there are certain bio-toxicities, and cannot promote on a large scale makes
With the quantum dot of, core-shell structure is due to its quantum efficiency height and bio-toxicity is small shows one's talent, it is widely used in by researchers
The detection of TNT.
In recent years, semiconductor-quantum-point luminescent material has attracted the interest of large quantities of researchers due to its excellent performance.
Zheng Yan pine in 2016 et al. disclose invented patent (CN201610401874.7) " one kind for explosive TNT test and analyze
Compound and preparation method thereof ".This method is folded formation molecule with the compound that explosive TNT detects, by three nitrogen piperazines by four
A tetraphenyl ethylene unit with aggregation-induced emission effect is formed by connecting, and suspension is gathered into 95% water/THF and is emitted
Hyperfluorescence.It is blasted in suspension when by the air for containing TNT gas, fluorescence can be quenched nearly 20%.1% is added in suspension
After NaCl, fluorescence can be quenched 50% or more, and the percentage being quenched is directly proportional to the air of the gas containing TNT blasted,
It can be used for the detection and analysis of TNT gas.Meanwhile the folded formation molecule can be used for the detection of TNT solution, sensitivity is up to several
A nM.Defend within 2014 it is deep and clear et al. disclose patent of invention (CN201410354353.1) " a kind of fluorescence detection aspirin
The preparation method of CdTe quantum ".First by caddy (CdCl2·2.5H2O), thiomalic acid (MSA) is mixed into certain pH
Aqueous solution, while by NaBH4It is mixed with Te powder, ultrasonic reaction generates NaHTe solution, flows back after then mixing the two anti-
It answers, generates the CdTe quantum of MSA modification.It is " a kind of that Sun Chun swallow in 2013 discloses patent of invention (CN201310185004.7)
Utilize the method for CdTe quantum fluorescence intensity detection organophosphorus pesticide ".The synthesis and purifying of cadmium telluride quantum dot aqueous solution；Benefit
With continuous colorimetric method observation the acephatemet containing various concentration CdTe system, with CdTe quantum Fluorescence Enhancement and
The colorimetric method that enzyme inhibits detects organophosphorus pesticide.Khiljas Irina Valerevna discloses patent of invention within 2010
(RU2010132746) " Biosensor for detecting 2,4,6-trinitrotoluene ".The disclosure of the invention one
The method that kind detects the 2,4,6-trinitrotoluene in different medium using yeast strain as sensor.It can using the vilolitin
The 2,4,6-trinitrotoluene for being 0.1 ~ 100mg/L with detectable concentration, and it is detectable in 4.5 ~ 8 pH value range.
Jose Almirall in 2009 etc. is open to have invented patent (US20090309016) " Method and apparatus for
detecting explosives".It is combined with ion mobility spectrometry with solid phase extraction, detection is labeled and the easy of concentration is waved
Hair property trace explosive is easy to be quick, sensitive cheap.Bradley in 2001 etc. is open to have invented patent (US2001011562)
The system of " Molecularly imprinted polymeric sensor for the detection of explosives "
Preparation Method.The preparation process of molecularly imprinted polymer explosives sensor is provided, the sensor is to explosive (2,4,6- tri- nitre
Base toluene (TNT) and 1,3,5- trinitrobenzens (TNB)) there is selection associativity.Polymer sensor includes porphyrin, works as polymer
When being exposed to explosive, detectable variation can be generated in the absorption of electromagnetic radiation and/or emission process, is reached to trace
The purpose of explosive detection.
But these methods are only to prepare CdTe quantum material, there are Cd for CdTe@CdS and CdTe quantum itself2+
Ion is easy to release generation cytotoxicity in quantum dot surface dissociation, this when oxidative environment and ultraviolet light irradiate
Effect is more obvious and the properties of external condition and quantum dot itself can all influence the stability of quantum dot, meanwhile,
The CdTe@CdS@ZnO quantum dot of nucleocapsid cladding has not been reported the detection of TNT, therefore, synthesizes highly selective and highly sensitive
Mercaptoethylmaine modification CdTe@CdS@ZnO quantum dot probe, simply and easily realize to ultra trace TNT molecular recognition and inspection
Survey has its necessity.
In the present invention, we report based on fluorescence resonance energy transfer principle in CdTe@CdS@ZnO quantum dot probe
Surface modification amino realizes the preparation method of the detection fluorescent test paper to trace TNT.Since TNT is gathered around, there are three electrophilic nitros
It is connected on aromatic rings, therefore, the TNT ten of electron deficient, which divides, to be easy to have an effect with the primary amine of electron rich, is formed Meisenheimer and is matched
Close object.When there is amido modified quantum dot mixing on TNT and surface, TNT can be adsorbed onto the surface of quantum dot, since TNT has
The aromatic rings of three electron-withdrawing group nitros, after quantum dot is optically excited, the electronics of ground state transition to high level holds very much
It is easily transferred on electrophilic aromatic rings, so as to cause the decline of the fluorescence intensity of quantum dot, quenches so as to cause quantum dot fluorescence
It goes out, is based on this principle, amido modified quantum dot can reach detection TNT and forming Meisenheimer complex with TNT
Purpose.Again since CdTe@CdS@ZnO quantum dot is especially suitable for as fluorescence probe, not only environmentally friendly, bio-toxicity
It is small, and CdTe@CdS@ZnO fluorescence probe surface can modify various functional groups (sulfydryl small molecule etc.) by coordination, use
In various detections.By this as a result, we are in CdTe@CdS@ZnO quantum dot fluorescence probe surface modification mercaptoethylmaine, amino
Charge-transfer complex can be formed with TNT target molecule, TNT target molecule is carried out based on fluorescence resonance energy transfer principle
Highly selective, high sensitivity detection.It possesses when one suitable fluorescent materials of selection fluorescence emission spectrum and TNT it is ultraviolet-
Visible absorption spectrum coincides, and when their spaces are close to each other, the fluorescence of fluorescent material will by Resonance energy transfer
It is absorbed by TNT, the fluorescence intensity of fluorescence probe is caused to decline, therefore, the fluorescence of CdTe@CdS@ZnO quantum dot will be had
Effect is quenched.It is strong to target molecule TNT combination sensibility that CdTe@CdS@ZnO quantum dot surface possesses amino unit, was detecting
Cheng Zhong can form quick response to target molecule TNT.About mercaptoethylmaine in CdTe@CdS@ZnO quantum dot surface modification, make
Its surface has the amino of mercaptoethylmaine.The CdTe@CdS@ZnO quantum dot of this surface modification mercaptoethylmaine is total by fluorescence
Minimum detection limit reaches 10 to vibration energy transfer in the liquid phase-11mol·L-1.This fluorescence to TNT molecule with the specially property known effect
CdTe@CdS@ZnO quantum dot, shows using quantum dot fluorescence as probe, mercaptoethylmaine as recognition site, by carrier of test paper
It detects to the highly selective of trace TNT, high sensitivity and easily.
Summary of the invention
Goal of the invention: for shortcoming existing for currently available technology, the present invention prepares mercaptoethylmaine cladding for the first time
CdTe@CdS@ZnO quantum dot, quantum dot surface have mercaptoethylmaine amino group, to trace TNT have identification function,
Fluorescence quantum realizes the detection to TNT by the change of fluorescence intensity.The preparation method is sulfydryl Aqueous phase, firstly,
Then the CdTe@CdS quantum dot of one-step synthesis mercaptoethylmaine modification coats ZnO on the surface@CdS CdTe by hydrolysis zinc acetate
Shell prepares CdTe@CdS@ZnO quantum dot, and to its surface modification functional group mercaptoethylmaine, finally, TNT detection is glimmering
The preparation of light test paper has obtained fluorescent test paper of a kind of couple of TNT with highly selective, high sensitivity, trace and easy detection.
The technical scheme is that a kind of preparation method of the fluorescent test paper for TNT detection, it is characterised in that: institute
The fluorescent test paper stated is immersed in chemical test paper by the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine
It constitutes, both the amino for the electron-donating group that quantum dot fluorescence probe surface possesses and the TNT of three electrophilic nitryl groups are empty
Between it is close to each other when, energy transfer occurs, is changed by the fluorescence intensity of CdTe@CdS@ZnO quantum dot fluorescence probe, it is real
Now to the detection of TNT, the preparation process of the fluorescent test paper includes following three step:
The first step is the preparation of CdTe@CdS quantum dot: firstly, distinguishing precise with the electronic balance that precision is a ten thousandth
0.0250 ~ 0.0270g tellurium powder and 0.0500 ~ 0.0700g sodium borohydride are placed in 50mL single-necked flask, then, then measure 9
~ 11mL deionized water is added in above-mentioned flask, in a nitrogen atmosphere, 50 ~ 60 DEG C of waters bath with thermostatic control, 400 ~ 600rpm
20 ~ 30min is stirred under revolving speed, solution colour gradually becomes darkviolet by black in reaction process, obtains presoma hydrogen telluride
Sodium solution, finally, the CdCl of 0.0910 ~ 0.0920g of precise again2·2.5H2O is placed in 100mL beaker, and addition 60 ~
The mercaptoethylmaine of the water of 80mL and 60 ~ 80 μ L constantly stirs with glass bar and is added the NaOH of 1 ~ 3mol/L, adjusts solution
PH value pours into resulting solution in 250mL three-necked flask in 8 ~ 10 ranges, is heated to reflux and is stirred continuously, takes simultaneously
3 ~ 5mL presoma sodium hydrogen telluride solution of above-mentioned preparation is quickly adding into above-mentioned three-necked flask out, solution by it is colourless by
It fades to light yellow, has obtained CdTe@CdS quantum dot；
Second step is the preparation of the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine: by above-mentioned preparation
CdTe CdS quantum dot heats in reflux unit, is separately added into the acetic acid of 0.1 mol/L of 10 ~ 20 μ L after reflux thereto
The mercaptoethylmaine of 0.03 mol/L of zinc solution and 20 ~ 40 μ L, are stirred continuously with 1400 ~ 1600 rpm revolving speeds, reaction 30
After ~ 40min, isopropanol and dehydrated alcohol ultrasonic disperse, eccentric cleaning is used respectively three times, to be dispersed in 90 ~ 110mL again respectively
In deionized water, the CdTe@CdS@ZnO quantum dot fluorescence probe that there is identification and detection function to target molecule is obtained；
Third step is the preparation for the fluorescent test paper of TNT detection: the chemical filter paper that diameter is 110mm is immersed in above-mentioned be made
CdTe@CdS@ZnO quantum dot fluorescence probe deionized water solution in, taken out after 9 ~ 11min, be protected from light naturally dry, cut
At different shape and size paper tape, the fluorescent test paper detected for target molecule has been obtained.
As a further improvement of existing technologies, in the preparation of the CdTe@CdS quantum dot, sulfydryl second used
Amine is stabilizer.In the preparation of the CdTe@CdS quantum dot, different emission spectrum face can be obtained by controlling the reaction time
The CdTe@CdS quantum dot of color.In the preparation of the fluorescent test paper, ZnO shell in CdTe@CdS@ZnO quantum dot fluorescence probe
It is that CdTe@CdS quantum dot surface is incorporated in by zinc acetate hydrolysis.In the preparation of the fluorescent test paper, CdTe@CdS@ZnO
The partial size and ZnO thickness of the shell of quantum dot fluorescence probe can be controlled by adjusting return time.The system of the fluorescent test paper
In standby, the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine, surface is rich in amino.The fluorescence examination
In the preparation of paper, the ZnO quantum dot fluorescence probe surface CdS@CdTe@has electronegativity.In the preparation of the fluorescent test paper
Target molecule is TNT.Detection is realized based on fluorescence resonance energy transfer principle in the preparation of the fluorescent test paper.
Compared with the existing technology the utility model has the advantages that
In recent years, the performance excellent due to semiconductor-quantum-point luminescent material attracts by research object of semiconductor nano material
The interest of large quantities of researchers.Zheng Yan pine in 2016 et al., which discloses, has invented a kind of patent (CN201610401874.7) " use
In the compound and preparation method thereof that explosive TNT tests and analyzes ".This method is folding with the compound that explosive TNT detects
Four tetraphenyl ethylene units with aggregation-induced emission effect are formed by connecting, in 95% water/THF by body molecule by three nitrogen piperazines
In be gathered into suspension and emit hyperfluorescence.It is blasted in suspension when by the air for containing TNT gas, fluorescence can be quenched closely
20%.After 1%NaCl is added in suspension, fluorescence can be quenched 50% or more, and the percentage that is quenched with blast
The air of the gas containing TNT is directly proportional, can be used for the detection and analysis of TNT gas.Meanwhile the folded formation molecule can be used for TNT
The detection of solution, sensitivity is up to several nM.It defends within 2014 and deep and clear et al. discloses patent of invention (CN201410354353.1) " one
The preparation method of the CdTe quantum of kind fluorescence detection aspirin ".First by caddy (CdCl2·2.5H2O), thio apple
Sour (MSA) is mixed into the aqueous solution of certain pH, while by NaBH4It is mixed with Te powder, ultrasonic reaction generates NaHTe solution, then
Back flow reaction after the two is mixed generates the CdTe quantum of MSA modification.Sun Chun swallow discloses patent of invention within 2013
(CN201310185004.7) " a method of organophosphorus pesticide is detected using CdTe quantum fluorescence intensity ".Cadmium telluride quantum
The synthesis and purifying of point aqueous solution；Using the CdTe system of acephatemet of the continuous colorimetric method observation containing various concentration, use
The colorimetric method that the Fluorescence Enhancement and enzyme of CdTe quantum inhibit detects organophosphorus pesticide.Khiljas Irina in 2010
Valerevna discloses patent of invention (RU2010132746) " Biosensor for detecting 2,4,6-
trinitrotoluene".A kind of 2,4,6- tri- detected using yeast strain as sensor in different medium of the disclosure of the invention
The method of nitrotoleune.It can detecte the 2,4,6-trinitrotoluene that concentration is 0.1 ~ 100mg/L using the vilolitin, and
PH value range 4.5 ~ 8 is detectable.Jose Almirall in 2009 etc. is open to have invented patent
(US20090309016) " Method and apparatus for detecting explosives ".With ion mobility spectrometry
It is combined with solid phase extraction, detection is labeled and the effumability trace explosive of concentration, easy to be quick, sensitive cheap.
Bradley in 2001 etc. is open to have invented patent (US2001011562) " Molecularly imprinted polymeric
The preparation method of sensor for the detection of explosives ".Provide molecularly imprinted polymer explosive
The preparation process of sensor, the sensor is to explosive (2,4,6-trinitrotoluene (TNT) and 1,3,5- trinitrobenzens (TNB))
With selection associativity.Polymer sensor includes porphyrin, when polymer is exposed to explosive, the absorption of electromagnetic radiation
And/or detectable variation can be generated in emission process, achieve the purpose that detect trace explosive.
But these methods are only to prepare CdTe quantum or polymer imprinted material, and its surface is not coated and repaired
Decorations, simultaneously because there are Cd for CdTe@CdS and CdTe quantum itself2+Ion is easy to release production in quantum dot surface dissociation
Raw cytotoxicity, when oxidative environment and ultraviolet light irradiate, this effect is more obvious and external condition and quantum dot sheet
The properties of body can all influence the stability of quantum dot, meanwhile, for the CdTe CdS ZnO of surface modification mercaptoethylmaine
Quantum dot fluorescence probe infiltrates in test paper, and realization has no that document gives report to the highly selective identification of TNT and easy detection,
Therefore, the CdTe@CdS@ZnO quantum dot fluorescence probe of highly selective, highly sensitive mercaptoethylmaine modification is synthesized, it is convenient to TNT
The fluorescent test paper preparation method of detection, realization have its necessity to ultra trace TNT molecular recognition and detection.
The first step of the present invention is the preparation of CdTe@CdS quantum dot: firstly, with the electronic balance that precision is a ten thousandth point
Other precise 0.0250 ~ 0.0270g tellurium powder and 0.0500 ~ 0.0700g sodium borohydride are placed in 50mL single-necked flask, so
Afterwards, it then measures 9 ~ 11mL deionized water and is added in above-mentioned flask, in a nitrogen atmosphere, 50 ~ 60 DEG C of waters bath with thermostatic control,
20 ~ 30min is stirred under 400 ~ 600rpm revolving speed, solution colour gradually becomes darkviolet by black in reaction process, obtains
Presoma sodium hydrogen telluride solution, finally, the CdCl of 0.0910 ~ 0.0920g of precise again2·2.5H2O is placed in 100mL beaker
In, the water of 60 ~ 80mL and the mercaptoethylmaine of 60 ~ 80 μ L is added, is constantly stirred with glass bar and is added 1 ~ 3mol/L's
NaOH adjusts solution ph in 8 ~ 10 ranges, resulting solution is poured into 250mL three-necked flask, is heated to reflux not
Disconnected stirring, while the 3 ~ 5mL presoma sodium hydrogen telluride solution for taking out above-mentioned preparation is quickly adding into above-mentioned three-necked flask,
Solution gradually becomes light yellow by colourless, has obtained CdTe@CdS quantum dot；
Second step is the preparation of the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine: by above-mentioned preparation
CdTe CdS quantum dot heats in reflux unit, is separately added into the acetic acid of 0.1 mol/L of 10 ~ 20 μ L after reflux thereto
The mercaptoethylmaine of 0.03 mol/L of zinc solution and 20 ~ 40 μ L, are stirred continuously with 1400 ~ 1600 rpm revolving speeds, reaction 30
After ~ 40min, isopropanol and dehydrated alcohol ultrasonic disperse, eccentric cleaning is used respectively three times, to be dispersed in 90 ~ 110mL again respectively
In deionized water, the CdTe@CdS@ZnO quantum dot fluorescence probe that there is identification and detection function to target molecule is obtained；
Third step is the preparation for the fluorescent test paper of TNT detection: the chemical filter paper that diameter is 110mm is immersed in above-mentioned be made
CdTe@CdS@ZnO quantum dot fluorescence probe deionized water solution in, taken out after 9 ~ 11min, be protected from light naturally dry, cut
At different shape and size paper tape, the fluorescent test paper detected for target molecule has been obtained.
In conclusion the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine, not only increases fluorescence and visits
The specific surface area of needle, and molecular recognition site is increased, bio-toxicity is also reduced, it is environmentally friendly, it improves selectivity, know
Other property and sensibility.
Second, the surface modification CdTe@CdS@ZnO quantum dot fluorescence probe of mercaptoethylmaine, it can be to TNT molecular selection
Property identification.After TNT target molecule enters test paper, the electron rich amino on CdTe@CdS@ZnO quantum dot fluorescence probe surface with
When TNT molecule is spatially close to each other, fluorescence can be based on electron deficient TNT by forming Meisenheimer complex
Resonance energy transfer principle, the emitted green light of CdTe@CdS@ZnO quantum dot can be absorbed in this complex, by under fluorescence intensity
Drop is realized and is detected to TNT.Synthetic surface is rich in the CdTe CdS ZnO quantum dot fluorescence probe of mercaptoethylmaine, while can also be with
Selectivity is used to detect other aromatic nitro explosive molecules, such as 2,4,6- trinitrophenols (2,4,6-Trinitrophenol,
Picric acid, PA), 2,4- dinitrotoluene (DNT) (2,4-dinitrotoluene, DNT).As it can be seen that side provided by the present invention
Method be it is general, usage range does not limit to the detection with a kind of explosive than wide.
Third, compared with traditional organic fluorescence materials, the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine
Fluorescence probe fluorescence lifetime is long, has biggish specific surface area, possesses more recognition site, improves to target molecule TNT's
Selective recognition improves the sensitive detection of the height to target analytes using fluorescence resonance energy transfer principle.
Fourth, the partial size and thickness of CdTe@CdS@ZnO quantum dot are controllable in method provided by the present invention, can pass through
Return time is controlled, and return time is longer, and partial size is bigger.
Fifth, the purpose of the CdTe@CdS@ZnO quantum dot of selection mercaptoethylmaine modification, because it has the advantage that
(1) CdTe@CdS@ZnO quantum dot fluorescence lifetime is long;(2) relatively easy, advantage of lower cost is synthesized under hydrothermal condition；(3) raw
Object toxicity is low；(4) surface is easy grafting organo-functional group；(5) environmental sound；(6) the CdTe@modified by mercaptoethylmaine
Meisenheimer complex, this complex and green fluorescence CdTe@CdS@ZnO quantum are formed between CdS@ZnO quantum dot and TNT
Fluorescence resonance energy transfer has occurred when space is close between point, by the decrease of fluorescence intensity, realizes to target analytes
The detection of TNT.
Detailed description of the invention
Fig. 1 is that the CdTe@CdS@ZnO quantum dot fluorescence probe synthesis of surface modification mercaptoethylmaine of the present invention is shown
It is intended to.
Fig. 2 be it is ultraviolet after differential responses time CdTe@CdS@ZnO quantum dot solution of the present invention normalization-can
See abosrption spectrogram (A) and corresponding fluorescence emission spectrogram of compound (B).That illustration indicates is differential responses time CdTe CdS ZnO
Quantum dot aqueous solution under natural light (a) and in the case where wavelength is the ultraviolet lamp of 254 nm (b) photo.
Fig. 3 is the XRD spectra of CdTe@CdS@ZnO quantum dot and CdTe@CdS quantum dot powder of the present invention.
Fig. 4 is the SEM figure of the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention.
Fig. 5 is the grain size distribution of the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention.
Fig. 6 is the surface charge distribution of the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention
Figure.
Fig. 7 is the CdTe@CdS@ZnO quantum dot and target molecule TNT of surface modification mercaptoethylmaine of the present invention
Between by fluorescence resonance energy transfer principle realize to TNT detection schematic diagram.
Fig. 8 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to TNT detection limit
Figure of fluorescence intensity changes.
Fig. 9 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to DNT detection limit
Figure of fluorescence intensity changes.
Figure 10 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to PA detection limit
Figure of fluorescence intensity changes.
Figure 11 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to various concentration TNT
Fluorescence spectrum variation diagram (A) and its corresponding fluorescent quenching constant figure (B).
Figure 12 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to various concentration DNT
Fluorescence spectrum variation diagram (A) and its corresponding fluorescent quenching constant figure (B).
Figure 13 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to various concentration PA
Fluorescence spectrum variation diagram (A) and its corresponding fluorescent quenching constant figure (B).
Figure 14 is fluorescent test paper of the present invention in the case where wavelength is the ultraviolet lamp of 254nm to without TNT(A is added dropwise) and drop
Add 10-11mol·L-1TNT(B the comparison of photo) is detected.
Specific embodiment is explained further with reference to the accompanying drawings
Fig. 1 is the CdTe@CdS@ZnO quantum dot fluorescence probe synthesis signal of surface modification mercaptoethylmaine of the present invention
Figure.The first step is the preparation of CdTe@CdS quantum dot in Fig. 1: firstly, accurate with the electronic balance difference that precision is a ten thousandth
It weighs 0.0250 ~ 0.0270g tellurium powder and 0.0500 ~ 0.0700g sodium borohydride is placed in 50mL single-necked flask, then, then
9 ~ 11mL deionized water is measured to be added in above-mentioned flask, in a nitrogen atmosphere, 50 ~ 60 DEG C of waters bath with thermostatic control, 400 ~
20 ~ 30min is stirred under 600rpm revolving speed, solution colour gradually becomes darkviolet by black in reaction process, obtains presoma
Sodium hydrogen telluride solution, finally, the CdCl of 0.0910 ~ 0.0920g of precise again2·2.5H2O is placed in 100mL beaker, is added
Enter the water of 60 ~ 80mL and the mercaptoethylmaine of 60 ~ 80 μ L, the NaOH of 1 ~ 3mol/L constantly stirred and be added with glass bar,
Solution ph is adjusted in 8 ~ 10 ranges, resulting solution is poured into 250mL three-necked flask, is heated to reflux and constantly stirs
It mixes, while the 3 ~ 5mL presoma sodium hydrogen telluride solution for taking out above-mentioned preparation is quickly adding into above-mentioned three-necked flask, solution
It gradually becomes light yellow by colourless, has obtained CdTe@CdS quantum dot；Second step is the CdTe@CdS@of surface modification mercaptoethylmaine
The preparation of ZnO quantum dot fluorescence probe: the CdTe CdS quantum dot of above-mentioned preparation is heated in reflux unit, to it after reflux
In be separately added into 10 ~ 20 μ L 0.1 mol/L acetic acid zinc solution and 20 ~ 40 μ L 0.03 mol/L mercaptoethylmaine,
It is stirred continuously with 1400 ~ 1600 rpm revolving speeds, after reacting 30 ~ 40min, respectively with isopropanol and dehydrated alcohol ultrasound point
Scattered, eccentric cleaning respectively three times, is dispersed in 90 ~ 110mL deionized water again, obtains having identification and detection to target molecule
The CdTe@CdS@ZnO quantum dot fluorescence probe of function.
Fig. 2 be it is ultraviolet after differential responses time CdTe@CdS@ZnO quantum dot solution of the present invention normalization-can
See abosrption spectrogram (A) and corresponding fluorescence emission spectrogram of compound (B).That illustration indicates is differential responses time CdTe CdS ZnO
Quantum dot aqueous solution under natural light (a) and in the case where wavelength is the ultraviolet lamp of 254 nm (b) photo.Reaction is from starting reflux
There is apparent structuring peak in the absorption spectrogram of reaction solution in a period of time, illustrates to form CdTe CdS ZnO nucleocapsid amount at this time
Sub-, the color of reaction solution also gradually becomes light yellow by colourless under natural light, as shown in illustration (a) in Fig. 2A.By scheming
It can be seen that the absorption spectrum of CdTe@CdS@ZnO core-shell quanta dots is gradually mobile to long wave direction with the growth of return time
(Red Shift Phenomena occurs), the structure peak of absorption peak also from the beginning is changed into acromion, the ruler of CdTe@CdS@ZnO core-shell quanta dots
Very little to be gradually increased, the size distribution of quantum dot gradually broadens, as shown in figure in Fig. 2A.CdTe@CdS@ZnO nucleocapsid quantum in Fig. 2 B
Point emission spectrum color from green, yellow green, yellow, it is orange-yellow become red, corresponding maximum emission wavelength is
525nm, 538nm, 555nm, 571nm and 601nm.It is the colorimetric in the case where wavelength is the ultraviolet lamp of 254nm shown in illustration (b) in Fig. 2 B
In ware the color of quantum dot emission fluorescence be successively green from left to right, it is yellow green, yellow, orange-yellow and red, it can be seen that
It is corresponding with the launch wavelength of maximum intensity in Fig. 2A.
Fig. 3 is the XRD spectra of CdTe@CdS@ZnO quantum dot and CdTe@CdS quantum dot powder of the present invention.Figure
What is respectively indicated in 3 is CdTe@CdS@ZnO quantum dot and CdTe@CdS quantum dot powder, the standard card (851267#) of CdTe
XRD spectrum by compared with the two XRD spectrum as can be seen that in 2 θ being about at 23, the peak of three essentially coincides, and can be inferred that
ZnO is successfully coated to CdTe@CdS quantum dot surface, and overall structure all keeps the cube structure of CdTe quantum.
Fig. 4 is the SEM figure of the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention.By putting
Big 400,000 times of SEM figure is it can be seen that graininess, partial size about 5nm or so is presented in the CdTe@CdS@ZnO particle of nucleocapsid structure.
Fig. 5 is the grain size distribution of the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention.
It can be seen that the CdTe@CdS@ZnO quantum dot particle diameter distribution of surface modification mercaptoethylmaine is between 2 ~ 10nm in Fig. 5, wherein
Most of particle diameter distribution is between 3 ~ 6nm.
Fig. 6 is the surface charge distribution of the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention
Figure.It can be seen that the CdTe@CdS@ZnO quantum dot distribution of charges range of surface modification mercaptoethylmaine is in 60 ~ 0 mV of ﹣ in Fig. 6
Between, wherein most quantum dot distribution of charges shows that CdTe@CdS@ZnO quantum dot surface is negatively charged in 25 mV of ﹣ or so.
Fig. 7 is the CdTe@CdS@ZnO quantum dot and target molecule TNT of surface modification mercaptoethylmaine of the present invention
Between by fluorescence resonance energy transfer principle realize to TNT detection schematic diagram.When target molecule TNT and surface have negative electrical charge
CdTe CdS ZnO quantum dot it is spatially close to each other when, charge can be passed through by gathering around the TNT there are three electrophilic nitryl group
Transferance adheres to the surface of CdTe@CdS@ZnO quantum dot, Meisenheimer complex is formed, as CdTe@CdS@ZnO
After quantum dot is optically excited, from the ground state transition of low-lying level to the excitation state of high level, the electronics of the excitation state of high level is non-
It is often easily transferred on electrophilic TNT aromatic rings, nonradiative fluorescence resonance energy transfer occurs, so as to cause CdTe@CdS@
The fluorescent quenching of ZnO quantum dot is realized to TNT molecular recognition and trace detection.
Fig. 8 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to TNT detection limit
Figure of fluorescence intensity changes.Eight parts of sample of@ZnO quantum dot fluorescence probe of the CdTe@CdS of 20 μ L is taken respectively, then is successively added dropwise respectively
Concentration is 0 molL-1、1×10-11mol·L-1、1×10-10mol·L-1、1×10-9mol·L-1、1×10-8mol·L-1、1
×10-7mol·L-1、1×10-6mol·L-1With 1 × 10-5mol·L-1TNT, obtained CdTe@CdS@ZnO quantum dot fluorescence
The fluorescence emission spectrum of probe change curve from top to bottom, it can be seen that with being continuously increased for TNT concentration, CdTe@CdS@ZnO
The fluorescence intensity of quantum dot obviously weakens, and shows CdTe@CdS@ZnO quantum dot surface modification amino-functional group and target point
Meisenheimer complex is formed when analysing spatially close to each other between object TNT, CdTe@CdS@ZnO quantum dot fluorescence is visited
Fluorescence resonance energy transfer occurs between needle and target analytes TNT effect, so that CdTe@CdS@ZnO quantum dot fluorescence be made to visit
The decline of needle fluorescence intensity, detection limit reach 1 × 10-11 mol·L-1, it is successfully realized to TNT identification and ultra trace detection.
Fig. 9 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to DNT detection limit
Figure of fluorescence intensity changes.Eight parts of sample of@ZnO quantum dot fluorescence probe of the CdTe@CdS of 20 μ L is taken respectively, then is successively added dropwise respectively
Concentration is 0 molL-1、1×10-9mol·L-1、1×10-8mol·L-1、1×10-7mol·L-1、1×10-6mol·L-1、1
×10-5mol·L-1、1×10-4mol·L-1With 1 × 10-3mol·L-1DNT, obtained CdTe@CdS@ZnO quantum dot fluorescence
The fluorescence emission spectrum of probe change curve from top to bottom, it can be seen that with being continuously increased for DNT concentration, CdTe@CdS@ZnO
The fluorescence intensity of quantum dot weakens, and shows CdTe@CdS@ZnO quantum dot surface modification amino-functional group and target analytes
It interacts when spatially close to each other between DNT, CdTe@CdS@ZnO quantum dot fluorescence probe and target analytes
Part fluorescence resonance energy transfer occurs between DNT effect, to make CdTe CdS ZnO quantum dot fluorescence probe fluorescence intensity
Decline, detection limit reach 1 × 10-9 mol·L-1, it is successfully realized to DNT identification and trace detection.
Figure 10 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to PA detection limit
Figure of fluorescence intensity changes.Eight parts of sample of@ZnO quantum dot fluorescence probe of the CdTe@CdS of 20 μ L is taken respectively, then is successively added dropwise respectively
Concentration is 0 molL-1、1×10-9mol·L-1、1×10-8mol·L-1、1×10-7mol·L-1、1×10-6mol·L-1、1
×10-5mol·L-1、1×10-4mol·L-1With 1 × 10-3mol·L-1PA, obtained CdTe@CdS@ZnO quantum dot fluorescence
The fluorescence emission spectrum of probe change curve from top to bottom, it can be seen that with being continuously increased for PA concentration, CdTe@CdS@ZnO
The fluorescence intensity of quantum dot obviously weakens, and shows CdTe@CdS@ZnO quantum dot surface modification amino-functional group and target point
It interacts when spatially close to each other between analysis object PA, CdTe@CdS@ZnO quantum dot fluorescence probe and target analysis
Fluorescence resonance energy transfer occurs between object PA effect, to make under CdTe@CdS@ZnO quantum dot fluorescence probe fluorescence intensity
Drop, detection limit reach 1 × 10-9 mol·L-1, it is successfully realized to PA identification and trace detection.
Figure 11 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to various concentration TNT
Fluorescence spectrum variation diagram (A) and its corresponding fluorescent quenching constant figure (B).From top to bottom it can be seen that with target in Figure 11 A
Analyte TNT concentration is from 0 molL-1、1×10-7mol·L-1、2×10-7mol·L-1、3×10-7mol·L-1、4×10- 7mol·L-1、5×10-7mol·L-1、6×10-7mol·L-1、7×10-7mol·L-1、8×10-7mol·L-1、9×10- 7mol·L-1Increase to 10 × 10-7mol·L-1, the fluorescence intensity of CdTe@CdS@ZnO quantum dot gradually weakens.According to Stern-
Volme equation: (I0/ I) -1=K sv·C TNT,I 0、IRespectively no target analytes and the stable state there are target analytes
Fluorescence intensity,K svFor the quenching constant of TNT,C TNTIndicate TNT solution concentration.According to the available TNT of Stern-Volme equation
Quenching constant be respectively as follows: 2812100Lmol-1。
Figure 12 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to various concentration DNT
Fluorescence spectrum variation diagram (A) and its corresponding fluorescent quenching constant figure (B).From top to bottom it can be seen that with target in Figure 12 A
Analyte DNT concentration is from 0molL-1、1×10-5mol·L-1、2×10-5mol·L-1、3×10-5mol·L-1、4×10- 5mol·L-1、5×10-5mol·L-1、6×10-5mol·L-1、7×10-5mol·L-1、8×10-5mol·L-1、9×10- 5mol·L-1Increase to 10 × 10-5mol·L-1, the fluorescence intensity of CdTe@CdS@ZnO quantum dot gradually weakens.According to Stern-
Volme equation: (I0/ I) -1=K sv·C DNT,I 0、IRespectively no target analytes and the stable state there are target analytes
Fluorescence intensity,K svFor the quenching constant of DNT,C DNTIndicate DNT solution concentration.According to the available DNT of Stern-Volme equation
Quenching constant be respectively as follows: 10615Lmol-1。
Figure 13 is the CdTe@CdS@ZnO quantum dot of surface modification mercaptoethylmaine of the present invention to various concentration PA
Fluorescence spectrum variation diagram (A) and its corresponding fluorescent quenching constant figure (B).From top to bottom it can be seen that with target in Figure 13 A
Analyte PA concentration is from 0molL-1、1×10-5mol·L-1、2×10-5mol·L-1、3×10-5mol·L-1、4×10- 5mol·L-1、5×10-5mol·L-1、6×10-5mol·L-1、7×10-5mol·L-1、8×10-5mol·L-1、9×10- 5mol·L-1Increase to 10 × 10-5mol·L-1, the fluorescence intensity of CdTe@CdS@ZnO quantum dot gradually weakens.According to Stern-
Volme equation: (I0/ I) -1=K sv·C PA,I 0、IRespectively no target analytes and there are the stable state of target analytes is glimmering
Luminous intensity,K svFor the quenching constant of PA,C PAIndicate PA solution concentration.According to the quenching of the available PA of Stern-Volme equation
Constant is respectively as follows: 4771Lmol-1。
Compared by Figure 11 B, 12B, 13B it can be concluded thatK sv, TNT>K sv, DNT>K sv, PA.This height being quenched is main
Absorbing wavelength model dependent on the complex that target analytes solution concentration and amino molecule form target analyte molecule
Enclose the degree Chong Die with CdTe@CdS@ZnO quantum dot fluorescence probe emission spectrum.As it can be seen that CdTe@CdS@ZnO quantum dot surface
More strong to the capture ability ratio DNT and PA of TNT molecule of amino, since there are three electrophilic in the molecular structure of TNT
Nitro can form Meisenheimer complex with the amino of electron rich, when close with quantum dot fluorescence probe space, occur
Fluorescence resonance energy transfer, to effectively realize fluorescent quenching.However, DNT possesses two nitros, although in PA molecular structure
There are three nitros, but PA is phenols, and comparatively electron-withdrawing ability is weaker, and formation Meisenheimer complex is more difficult, because
This, the two to CdTe CdS ZnO quantum dot fluorescence probe that efficiency ratio TNT is quenched is far short of what is expected.
Figure 14 is fluorescent test paper of the present invention in the case where wavelength is the ultraviolet lamp of 254nm to without TNT(A is added dropwise) and drop
Add 10-11mol·L-1TNT(B the comparison of photo) is detected.CdTe@CdS@ZnO quantum dot fluorescence probe, which is immersed in test paper, to be obtained
For TNT detection fluorescent test paper, be cut into English alphabet HFUU, what Figure 14 was respectively indicated be without be added dropwise TNT(A) and
It is added dropwise 10-11mol·L-1TNT(B photo of the fluorescent test paper of HFUU shape) in the case where wavelength is the ultraviolet lamp of 254 nm, passes through
The green emitted fluorescence intensity for comparing figure (A) is significantly stronger than the fluorescence intensity of figure (B), shows that this fluorescent test paper has to target
The function of molecule TNT identification and detection, this fluorescent test paper, which simply, can be realized easily, to be identified TNT and detects.
A kind of specific embodiment: preparation method of the fluorescent test paper for TNT detection, it is characterised in that: described is glimmering
Light test paper is to be immersed in chemical test paper to constitute by the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine, amount
Both the amino for the electron-donating group that son point fluorescence probe surface possesses and the TNT of three electrophilic nitryl groups space phase mutual connection
When close, energy transfer occurs, is changed by the fluorescence intensity of CdTe@CdS@ZnO quantum dot fluorescence probe, realizes to TNT
Detection, the preparation process of the fluorescent test paper includes following three step:
The first step is the preparation of CdTe@CdS quantum dot: firstly, distinguishing precise with the electronic balance that precision is a ten thousandth
0.0250 ~ 0.0270g tellurium powder and 0.0500 ~ 0.0700g sodium borohydride are placed in 50mL single-necked flask, then, then measure 9
~ 11mL deionized water is added in above-mentioned flask, in a nitrogen atmosphere, 50 ~ 60 DEG C of waters bath with thermostatic control, 400 ~ 600rpm
20 ~ 30min is stirred under revolving speed, solution colour gradually becomes darkviolet by black in reaction process, obtains presoma hydrogen telluride
Sodium solution, finally, the CdCl of 0.0910 ~ 0.0920g of precise again2·2.5H2O is placed in 100mL beaker, and addition 60 ~
The mercaptoethylmaine of the water of 80mL and 60 ~ 80 μ L constantly stirs with glass bar and is added the NaOH of 1 ~ 3mol/L, adjusts solution
PH value pours into resulting solution in 250mL three-necked flask in 8 ~ 10 ranges, is heated to reflux and is stirred continuously, takes simultaneously
3 ~ 5mL presoma sodium hydrogen telluride solution of above-mentioned preparation is quickly adding into above-mentioned three-necked flask out, solution by it is colourless by
It fades to light yellow, has obtained CdTe@CdS quantum dot；
Second step is the preparation of the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine: by above-mentioned preparation
CdTe CdS quantum dot heats in reflux unit, is separately added into the acetic acid of 0.1 mol/L of 10 ~ 20 μ L after reflux thereto
The mercaptoethylmaine of 0.03 mol/L of zinc solution and 20 ~ 40 μ L, are stirred continuously with 1400 ~ 1600 rpm revolving speeds, reaction 30
After ~ 40min, isopropanol and dehydrated alcohol ultrasonic disperse, eccentric cleaning is used respectively three times, to be dispersed in 90 ~ 110mL again respectively
In deionized water, the CdTe@CdS@ZnO quantum dot fluorescence probe that there is identification and detection function to target molecule is obtained；
Third step is the preparation for the fluorescent test paper of TNT detection: the chemical filter paper that diameter is 110mm is immersed in above-mentioned be made
CdTe@CdS@ZnO quantum dot fluorescence probe deionized water solution in, taken out after 9 ~ 11min, be protected from light naturally dry, cut
At different shape and size paper tape, the fluorescent test paper detected for target molecule has been obtained.
Embodiment: the fluorescent test paper for TNT detection is prepared using three-step approach.
The first step is the preparation of CdTe@CdS quantum dot: firstly, accurate with the electronic balance difference that precision is a ten thousandth
It weighs 0.0260g tellurium powder and 0.0600g sodium borohydride is placed in 50mL single-necked flask, then, then measure 10mL deionized water and add
Enter into above-mentioned flask, in a nitrogen atmosphere, 25min is stirred in 55 DEG C of waters bath with thermostatic control under 500rpm revolving speed, molten in reaction process
Liquid color gradually becomes darkviolet by black, obtain presoma sodium hydrogen telluride solution, finally, precise 0.0915g again
CdCl2·2.5H2O is placed in 100mL beaker, and the water of 70mL and the mercaptoethylmaine of 70 μ L is added, is constantly stirred and is added with glass bar
The NaOH for entering 2mol/L, makes pH value of solution=9, and resulting solution is poured into 250mL three-necked flask, is heated to reflux and constantly stirs
It mixes, while the 4mL presoma sodium hydrogen telluride solution for taking out above-mentioned preparation is quickly adding into above-mentioned three-necked flask, solution is by nothing
Color gradually becomes light yellow, has obtained CdTe@CdS quantum dot；
Second step is the preparation of the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine: by above-mentioned preparation
CdTe CdS quantum dot heats in reflux unit, and the zinc acetate for being separately added into 0.1 mol/L of 15 μ L after reflux thereto is molten
The mercaptoethylmaine of 0.03 mol/L of liquid and 30 μ L, are stirred continuously with 1500 rpm revolving speeds, after reacting 35min, use isopropyl respectively
Pure and mild dehydrated alcohol ultrasonic disperse, eccentric cleaning respectively three times, are dispersed in 100mL deionized water again, obtain to target molecule
CdTe@CdS@ZnO quantum dot fluorescence probe with identification and detection function；
Third step is the preparation for the fluorescent test paper of TNT detection: the chemical filter paper that diameter is 110mm is immersed in above-mentioned be made
CdTe@CdS@ZnO quantum dot fluorescence probe deionized water solution in, taken out after 10min, be protected from light naturally dry, be cut into not
Similar shape and size paper tape have obtained the fluorescent test paper detected for target molecule TNT.
Claims (9)
1. a kind of preparation method of the fluorescent test paper for TNT detection, it is characterised in that: the fluorescent test paper is repaired by surface
The CdTe@CdS@ZnO quantum dot fluorescence probe of decorations mercaptoethylmaine, which is immersed in chemical test paper, to be constituted, quantum dot fluorescence probe surface
When the space both TNT of the amino of the electron-donating group possessed and three electrophilic nitryl groups is close to each other, energy occurs and turns
It moves, is changed by the fluorescence intensity of CdTe@CdS@ZnO quantum dot fluorescence probe, realize the detection to TNT, described is glimmering
The preparation process of light test paper includes following three step: 1.1 first steps are the preparations of CdTe@CdS quantum dot: firstly, using precision
0.0250 ~ 0.0270g of precise tellurium powder and 0.0500 ~ 0.0700g hydroboration are distinguished for the electronic balance of a ten thousandth
Sodium is placed in 50mL single-necked flask, then, then is measured 9 ~ 11mL deionized water and is added in above-mentioned flask, in nitrogen atmosphere
Under, 20 ~ 30min is stirred in 50 ~ 60 DEG C of waters bath with thermostatic control under 400 ~ 600rpm revolving speed, and solution colour is by black in reaction process
Color gradually becomes darkviolet, obtain presoma sodium hydrogen telluride solution, finally, 0.0910 ~ 0.0920g of precise again
CdCl2·2.5H2O is placed in 100mL beaker, and the water of 60 ~ 80mL and the mercaptoethylmaine of 60 ~ 80 μ L is added, constantly uses glass
Stick stirs and is added the NaOH of 1 ~ 3mol/L, adjusts solution ph in 8 ~ 10 ranges, resulting solution is poured into 250mL
It in three-necked flask, is heated to reflux and is stirred continuously, while the 3 ~ 5mL presoma sodium hydrogen telluride solution for taking out above-mentioned preparation is rapid
It is added in above-mentioned three-necked flask, solution gradually becomes light yellow by colourless, has obtained CdTe@CdS quantum dot；
1.2 second steps are the preparations of the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine: by above-mentioned preparation
CdTe CdS quantum dot heated in reflux unit, the second of 0.1 mol/L of 10 ~ 20 μ L is separately added into after reflux thereto
The mercaptoethylmaine of 0.03 mol/L of sour zinc solution and 20 ~ 40 μ L, are stirred continuously with 1400 ~ 1600 rpm revolving speeds, reaction
After 30 ~ 40min, respectively respectively three times with isopropanol and dehydrated alcohol ultrasonic disperse, eccentric cleaning, it is dispersed in 90 again ~
In 110mL deionized water, the CdTe@CdS@ZnO quantum dot fluorescence probe that there is identification and detection function to target molecule is obtained；
1.3 third steps are the preparations for the fluorescent test paper of TNT detection: the chemical filter paper that diameter is 110mm being immersed in above-mentioned
In CdTe@CdS@ZnO quantum dot fluorescence probe deionized water solution obtained, is taken out after 9 ~ 11min, is protected from light naturally dry,
It is cut into different shape and size paper tape, has obtained the fluorescent test paper detected for target molecule.
2. the preparation method of a kind of fluorescent test paper for TNT detection according to claim 1, it is characterized in that: described
In the preparation of CdTe@CdS quantum dot, mercaptoethylmaine used is stabilizer.
3. the preparation method of a kind of fluorescent test paper for TNT detection according to claim 1, it is characterized in that: described
In the preparation of CdTe@CdS quantum dot, the CdTe@CdS quantum of different emission spectrum colors can be obtained by controlling the reaction time
Point.
4. the preparation method of a kind of fluorescent test paper for TNT detection according to claim 1, it is characterized in that: described
In the preparation of fluorescent test paper, ZnO shell is incorporated in by zinc acetate hydrolysis in CdTe@CdS@ZnO quantum dot fluorescence probe
CdTe@CdS quantum dot surface.
5. the preparation method of a kind of fluorescent test paper for TNT detection according to claim 1, it is characterized in that: described
In the preparation of fluorescent test paper, the partial size and ZnO thickness of the shell of CdTe@CdS@ZnO quantum dot fluorescence probe can be flowed back by adjusting
Time controls.
6. the preparation method of a kind of fluorescent test paper for TNT detection according to claim 1, it is characterized in that: described
In the preparation of fluorescent test paper, the CdTe@CdS@ZnO quantum dot fluorescence probe of surface modification mercaptoethylmaine, surface is rich in amino.
7. the preparation method of a kind of fluorescent test paper for TNT detection according to claim 1, it is characterized in that: described
In the preparation of fluorescent test paper, the ZnO quantum dot fluorescence probe surface CdS@CdTe@has electronegativity.
8. the preparation method of a kind of fluorescent test paper for TNT detection according to claim 1, it is characterized in that: described
Target molecule in the preparation of fluorescent test paper is TNT.
9. the preparation method of a kind of fluorescent test paper for TNT detection according to claim 1, it is characterized in that: described
Detection is realized based on fluorescence resonance energy transfer principle in the preparation of fluorescent test paper.
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